@article{2-s2.0-85192347284,

title = {Bloomery iron production in the Holy Cross Mountains (Poland) area during the Roman period: conditions during the metallurgical process and their uniformity between locations},

author = { K. Kupczak and R. Warchulski and A. Gawęda and Jan. Janiec},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85192347284&doi=10.1186%2fs40494-024-01266-6&partnerID=40&md5=4388d257b10f00046f3f1595b5155f32},

doi = {10.1186/s40494-024-01266-6},

issn = {20507445},

year  = {2024},

date = {2024-01-01},

journal = {Heritage Science},

volume = {12},

number = {1},

publisher = {Springer Science and Business Media Deutschland GmbH},

abstract = {The study assessed the uniformity of the metallurgical process carried out during the period of Roman influence in Poland. The age of the investigated material was confirmed based on an analysis of the 12C/14C isotope ratio in the charcoal found in slag. The comparison was based on four Holy Cross Mountains (Poland) locations. The evaluation included smelting temperature, viscosity of the metallurgical melt, oxidation–reduction conditions, and slag cooling rate determined based on geochemical (XRF) and mineralogical (XRD; SEM; EPMA) analyses. Despite the distance between individual sampling sites, the conditions in which smelting was carried out were similar for all samples. The liquidus temperature of the analyzed slags was in the range of 1150–1200 °C. Oxidation–reduction conditions were determined through thermodynamic calculations using SLAG software. In the temperature range of 1150–1200 °C, the oxygen fugacity had to be below logP O2 = − 13.20 to − 12.53 atm to reduce iron oxides to metallic iron. The viscosity of the metallurgical melt was calculated and ranged from 0.15 to 1.02 Pa s, indicating a low viscosity. The slag cooling rate determined based on olivine morphology was in the range of > 5 to 300 °C/h. Smelting parameters were compared with other locations in Poland, and similar results were obtained for slags from Masovia and Tarchlice. In the case of one site (Opole), despite the higher maximum value of liquidus temperature, it was indicated that the process could have taken place in similar conditions, and the differences resulted from contamination of the slag with material from the furnace/pit walls. © The Author(s) 2024.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85185124092,

title = {The use of predominance area diagrams (PAD) to determine the oxygen and sulfur fugacities prevailing during historical metallurgical processes: the case of fifteenth to seventeenth century copper slags from Polichno (Old Polish industrial district)},

author = { K. Kupczak and R. Warchulski and A. Gawęda and M. Ślęzak and P. Migas},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85185124092&doi=10.1186%2fs40494-024-01171-y&partnerID=40&md5=e3ccb8a809b2437b135efee3c2b40acd},

doi = {10.1186/s40494-024-01171-y},

issn = {20507445},

year  = {2024},

date = {2024-01-01},

journal = {Heritage Science},

volume = {12},

number = {1},

publisher = {Springer Science and Business Media Deutschland GmbH},

abstract = {The study presents the first use of predominance area diagrams (PADs) to determine oxidation–reduction conditions during reconstructing historical copper smelting processes. The smelting temperature and oxygen and sulfur fugacities during smelting were determined based on experiments and the geochemical (ICP-MS/ES; XRF) and mineralogical (SEM; EPMA) analyses of the fifteenth to seventeenth century slags from Polichno (Holy Cross Mountains; Poland). Results obtained during high-temperature experiments allowed to determine the slags' solidus and liquidus temperatures. The liquidus temperature was in the range of 1100–1200 °C, and the solidus temperature was in the range of 800–1100 °C. Data on temperature conditions were used in thermodynamic calculations to construct predominance area diagrams and then to determine the ranges of oxygen and sulfur fugacities in which the formation of slags was possible. Slags from Polichno were formed with the oxygen fugacity in the range of logPO2 = − 4.30 (POL1; POL4 at 1200 °C) to − 14.08 atm. (POL3 at 1090 °C). In turn, the sulfur fugacity during slag formation ranged from logPS2 = − 2.50 (POL5 at 1200 °C) to − 6.92 (POL4 at 1060 °C) atm. The relatively high sulfur availability confirms using sulfide ores without prior roasting. The wide range of sulfur and oxygen fugacity indicates the process's heterogeneity. © The Author(s) 2024.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85182440245,

title = {SLAG—software for reconstruction of historical smelting processes based on slag properties},

author = { K. Kupczak and R. Warchulski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85182440245&doi=10.1111%2farcm.12940&partnerID=40&md5=ad922b3d333d71ed87b15767f686eb90},

doi = {10.1111/arcm.12940},

issn = {0003813X},

year  = {2024},

date = {2024-01-01},

journal = {Archaeometry},

volume = {66},

number = {4},

pages = {803-823},

publisher = {John Wiley and Sons Inc},

abstract = {The publication presents the functions of the SLAG software created to recreate historical metallurgical processes. SLAG allows for determining the smelting temperature, the viscosity of the metallurgical melt, and the oxygen and sulfur fugacities during smelting. With software, both liquidus temperature and melt viscosity can be calculated using different models, covering the range of chemical compositions of historical slags as wide as possible. Based on thermodynamic calculations, SLAG allows the performance of O2 and S2 fugacity calculations in the temperature range of 1000–2000 K (727–1727°C). The range of applicability of other properties (viscosity and liquidus temperature) depends only on the limitations of individual models. Using SLAG, it is also possible to create predominance area diagrams (PADs) and diagrams that consider the viscosity's dependence on temperature for slag of a given chemical composition. Based on glass transition temperature (Tg) and melt fragility, it is also possible to reconstruct the conditions that prevailed during the various stages of historical glass manufacturing processes. © 2024 The Authors. Archaeometry © 2024 University of Oxford.},

note = {1},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85195457642,

title = {In-depth study of a speiss/matte sample from Castillo de Huarmey, North Coast of Peru, and its implications for the pre-Columbian production of arsenic bronze in the Central Andes},

author = { R. Warchulski and M. Kałaska and B.C. Rizzuto and P. Sierpień and M. Pisarek and G. Kaproń and B. Marciniak-Maliszewska and P. Jokubauskas and J. Kotowski and D. Środek and P. Prządka-Giersz and M. Giersz},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85195457642&doi=10.1111%2farcm.13000&partnerID=40&md5=6bfd44c1f221104dd3de2aebee50866c},

doi = {10.1111/arcm.13000},

issn = {0003813X},

year  = {2024},

date = {2024-01-01},

journal = {Archaeometry},

publisher = {John Wiley and Sons Inc},

abstract = {This study aims to characterize the phase composition and chemistry of the speiss/matte sample from the Metallurgist's Burial at Castillo de Huarmey and to use the information derived from these analyses to infer the temperatures, furnace conditions, and ores associated with the smelting processes, which created the speiss/matte sample. For this purpose, a number of geochemical analyses were performed on the spies/matte fragment: analysis of the general chemical composition (handheld X-ray fluorescence spectrometry [hhXRF]; X-ray photoelectron spectroscopy [XPS]), analysis of the chemical composition in the micro area (field emission scanning electron microscope with an energy dispersive spectroscopy detector [FE-SEM-EDS]; field emission electron probe microanalysis [FE-EPMA]), analysis of the mineral composition (X-ray diffraction [XRD]), and analysis of the phase composition (Raman spectroscopy). Chemical and mineralogical analyses of the speiss/matte specimen determined that the specimen is composed of distinct arsenide, arsenate, sulfide, and glass phases. During the smelting process, the charge material consisted mainly of Cu, Fe, and As sulfides. Arsenopyrite is the most likely candidate as the mineral source of arsenic. In addition, temperatures of at least 1200°C were achieved during the smelting process, with smelting occurring over a relatively short timeframe given that effective density separation of speiss and matte phases was not achieved. © 2024 The Author(s). Archaeometry © 2024 University of Oxford.},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85142055229,

title = {Reconstruction of smelting conditions during 16th- to 18th-century copper ore processing in the Kielce region (Old Polish Industrial District) based on slags from Miedziana Góra, Poland},

author = { K. Kupczak and R. Warchulski and A. Gawęda},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85142055229&doi=10.1111%2farcm.12837&partnerID=40&md5=4d28d5534a7f7c1dbcce97e0c7ea289d},

doi = {10.1111/arcm.12837},

issn = {0003813X},

year  = {2023},

date = {2023-01-01},

journal = {Archaeometry},

volume = {65},

number = {3},

pages = {547-569},

publisher = {John Wiley and Sons Inc},

abstract = {This study presents the first reconstruction of the smelting conditions in 16th- to 18th-century smelters from Miedziana Góra (Holy Cross Mountains; Poland). Based on geochemical (inductively coupled plasma mass spectrometry/emission spectrometry; X-ray fluorescence) and mineralogical analysis (X-ray diffractometry; scanning electron microscopy; electron probe micro-analysis) of historical slags, their chemical/phase composition and the basic smelting parameters (temperature; melt viscosity; and oxygen fugacity) were determined. Due to the differences in chemical and phase composition, slags from different smelting stages have been distinguished: hypocrystalline slags (MG6) from speiss/matte production and glassy (MG1–MG5) from matte conversion. In glassy slags, pyroxenes, quartz/cristobalite grains, and aggregates composed of metallic Cu and PbO are dispersed in the glass. Hypocrystalline slags are composed of wollastonites, anorthites, and metallic Cu. The temperature range at which the slags were formed was from ~1100°C (solidus temperature) to 1150–1200°C (liquidus temperature). The silicate melt's viscosity was from log η = 1.19 to 4.42 Pa s (at 1100–1200°C). The higher viscosity of MG1–MG5 slags indicates that, unlike MG6 slags, they were not formed during gravity separation. Information about the phase composition made it possible to determine the oxygen fugacity in the range of log fO2 = −4 to −12 atm. High oxygen fugacity indicates the oxidizing nature of the smelting process. © 2022 The Authors. Archaeometry published by John Wiley & Sons Ltd on behalf of University of Oxford.},

note = {1},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85123678976,

title = {Complete reconstruction of the process and conditions during gold smelting in the 15th–17th centuries in Złoty Stok based on metallurgical slags},

author = { R. Warchulski and K. Kupczak and A. Gawęda and R. Sitko},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85123678976&doi=10.1111%2farcm.12752&partnerID=40&md5=42bca27f554fb8d49e9fa8c42bfef052},

doi = {10.1111/arcm.12752},

issn = {0003813X},

year  = {2022},

date = {2022-01-01},

journal = {Archaeometry},

volume = {64},

number = {4},

pages = {916-934},

publisher = {John Wiley and Sons Inc},

abstract = {This study presents the first complete reconstruction of gold metallurgy in Złoty Stok, Poland. The key parameters of the process (i.e.; temperature of smelting and solidification; melt viscosity; oxygen fugacity) are calculated using the remnants of the process: metallurgical slags. The slags consist of silicate phases (i.e.; olivine; pyroxene), sulfides and arsenides (i.e.; pyrrhotite; Fe2As), as well as glass. These slags are chemically dominated by SiO2 (< 56.60 wt%), MgO (< 18.36 wt%), FeO (< 15.36 wt%), and CaO (< 15.19 wt%). The obtained results indicate that the temperature during the metallurgical process was at least 1300–1350°C, and crystallization of the slags took place until they cooled to < 1200°C. The morphology of olivine crystals in the slags indicates large differences in their cooling rate, from 5 to 300°C/h. Strongly reducing conditions during the metallurgical process (−10.5 to −11.5 log fO2) was confirmed. Low melt viscosity (logƞ = 0.26 – 0.90 Pa s) facilitated the separation of the sulfide melt rich in gold from the silicate melt being the slag precursor. The obtained results allowed existing descriptions of the smelting process in Złoty Stok to be corrected. © 2022 The Authors. Archaeometry © 2022 University of Oxford.},

note = {2},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85096435753,

title = {Reconstruction of 16th—17th century lead smelting processes on the basis of slag properties: A case study from Sławków, Poland},

author = { R. Warchulski and M. Szczuka and K. Kupczak},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85096435753&doi=10.3390%2fmin10111039&partnerID=40&md5=972b738db3377bf32e595be4ef532f4f},

doi = {10.3390/min10111039},

issn = {2075163X},

year  = {2020},

date = {2020-01-01},

journal = {Minerals},

volume = {10},

number = {11},

pages = {1-19},

publisher = {MDPI AG},

abstract = {The study focuses on the reconstruction of the technological process in the 16th–17th century lead smelter in Sławków based on chemical and petrographic analyzes of slags. There are three main types of material at the landfill: glassy, crystalline, and weathered. Glassy slags are made of amorphous phase in which crystals of pyroxene, willemite, olivine, wüstite, and lead oxide appear. Crystalline slags are composed of wollastonite, rankinite, melilite, anorthite, quartz, and Fe oxides. Weathered slags have a composition similar to glassy slags, but they also contain secondary phases: anglesite and cerussite. Chemical analyzes confirmed that the smelter used sulphide ores, which were roasted, and the main addition to the charge was quartz sand. The smelting process took place in a brick-built furnace, under reducing conditions, with varied oxygen fugacity ranging from WM to MH buffer. The slag characteristics show a knowledge of the workers in the field of smelting methods. The addition of SiO2 allowed for the binding of elements that could contaminate the obtained lead, and at the same time, the low melting point of the material (1150 ©C) and the melt viscosity (logη = 1.34 for 1150 ©C) was maintained, enabling the effective separation of liquid lead. © 2020 by the authors. Licensee MDPI, Basel, Switzerland.},

note = {5},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85095948455,

title = {Chemical and phase reactions on the contact between refractory materials and slags, a case from the 19th century zn-pb smelter in ruda Ślaska,˛ poland},

author = { K. Kupczak and R. Warchulski and M. Dulski and D. Środek},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85095948455&doi=10.3390%2fmin10111006&partnerID=40&md5=a43021871c7eb5dddbdab82c348ebcec},

doi = {10.3390/min10111006},

issn = {2075163X},

year  = {2020},

date = {2020-01-01},

journal = {Minerals},

volume = {10},

number = {11},

pages = {1-19},

publisher = {MDPI AG},

abstract = {Slags from the historic metallurgy of Zn-Pb ores are known for unique chemical and phase compositions. The oxides, silicates, aluminosilicates, and amorphous phases present therein often contain in the structure elements that are rare in natural conditions, such as Zn, Pb, As. The study focuses on processes occurring on the contact of the melted batch and the refractory materials that build the furnace, which lead to the formation of these phases. To describe them, chemical (X-ray fluorescence (XRF); inductively coupled plasma mass spectrometry (ICP-MS)) and petrological ((X-ray diffraction (XRD); electron probe micro-analyses (EPMA); Raman spectroscopy) analyses were performed on refractory material; slag; and contact of both. Two main types of reactions have been distinguished: gas/fluid-refractories and liquid-refractories. The first of them enrich the refractories with elements that migrate with the gas (Pb; K; Na; As; Zn) and transport the components building it (Fe; Mg; Ca) inward. Reactions between melted batch and refractory materials through gravitational differentiation and the melting of refractories lead to the formation of an aluminosilicate liquid with a high content of heavy elements. Cooling of this melt causes crystallization of minerals characteristic for slag; but with a modified composition; such as Fe-rich pyroxenes; Pb-rich K-feldspar; or PbO-As2 O3-SiO2 glass. © 2020 by the authors. Licensee MDPI; Basel; Switzerland.},

note = {3},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85088039706,

title = {Slags from Ruda Śląska, Poland as a large-scale laboratory for the crystallization of rare natural rocks: melilitolites and paralavas},

author = { R. Warchulski and A. Gawęda and K. Kupczak and K. Banasik and T. Krzykawski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85088039706&doi=10.1016%2fj.lithos.2020.105666&partnerID=40&md5=9d90e3fec170517c9d23826f6d133b03},

doi = {10.1016/j.lithos.2020.105666},

issn = {00244937},

year  = {2020},

date = {2020-01-01},

journal = {Lithos},

volume = {372-373},

publisher = {Elsevier B.V.},

abstract = {Zinc and lead smelting slags from Ruda Śląska are unique in their chemistry and phase composition, which resemble rare natural rocks such as paralavas and melilitolites. Moreover, considering its size, we can treat a pyrometallurgical slag dump as a geological body. In slags from Ruda Śląska the assemblage melilite ± pseudowollastonite ± wollastonite ± plagioclase was discovered in glassy slag. High-temperature experiments were performed to determine the temperature conditions and to reconstruct the crystallization of such an assemblage. Two slag samples were subjected to complete melting and crystallization with controlled thermal gradients of: 53.25 °C/h, 15.20 °C/h and 7.60 °C/h. The results showed that crystal nucleation started at temperatures of 1250-1300 °C depending on the fluctuations of chemical composition. In both samples the thermal gradient only partly influenced the phase differentiation, being rather responsible for the disappearance of the primary glass. Moreover, even slight differences in chemical composition resulted in changes in phase assemblages under the same temperature conditions (mll + gls vs pwol+pl + mll + gls). It was proven that it is due to the combination of undercooling conditions and solidus dependences in the åkermanite – gehlenite solid solution. The occurrence of such phenomena should be considered in natural rocks with similar composition. In the case of the Ruda Śląska slags it explains the dominance of glassy slag in that location. The experiments gave us an opportunity to observe and precisely analyze crystallization in real time, providing new insights into the creation of slags and their natural analogues. However, the study has also shown that possible variations of the original crystallization should always be assessed. © 2020 Elsevier B.V.},

note = {3},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85086904396,

title = {Geophysical and petrological studies of the former lead smelting waste dump in Sławków, Poland},

author = { M.J. Mendecki and R. Warchulski and M. Szczuka and D. Środek and J. Pierwoła},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85086904396&doi=10.1016%2fj.jappgeo.2020.104080&partnerID=40&md5=8df2f22f0c5fcc6ef471881c79ab1364},

doi = {10.1016/j.jappgeo.2020.104080},

issn = {09269851},

year  = {2020},

date = {2020-01-01},

journal = {Journal of Applied Geophysics},

volume = {179},

publisher = {Elsevier B.V.},

abstract = {The city of Sławków has witnessed the metallurgical industry from the Middle Ages to modern times. The lead smelting causes usually contamination by a slag waste dump, threatening the environment of the vicinity of the cities. Similar industry existed in many places around the world but, so far, no geophysical work has ever been reported to deal with this problem. In this paper, we present the results of the electromagnetic (EM) and electrical resistivity tomography (ERT) measurements, and petrological (XRD; EPMA; SEM-EDS) tests in order to identify the extent of the slag waste dump and pollution leaching. The geophysical method allowed to identify the spatial distribution, ERT – depths, whereas EM – lateral distribution. Moreover, these studies provide information about the electrical properties of the slags, i.e. conductivity and in-phase component. The field surveys were supplemented by petrological analyses using EPMA, SEM-EDS and XRD. These allowed to determine the phase composition and chemistry of the slag. Together with EM and ERT measurements, it allowed to illustrate the lack of pollution transfer to soils caused by the slag presence in the studied area. © 2020},

note = {5},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85078022204,

title = {Pb-rich slags, minerals, and pollution resulted from a medieval ag-pb smelting and mining operation in the silesian-cracovian region (Southern Poland)},

author = { J. Cabała and R. Warchulski and D. Rozmus and D. Środek and E. Szełęg},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85078022204&doi=10.3390%2fmin10010028&partnerID=40&md5=e853fb643c36e962c86bf6971b152461},

doi = {10.3390/min10010028},

issn = {2075163X},

year  = {2020},

date = {2020-01-01},

journal = {Minerals},

volume = {10},

number = {1},

publisher = {MDPI AG},

abstract = {Since the 12th century in the Silesian-Cracovian area, lead, litharge, and silver have been produced by the pyrometallurgical processing of Pb-Ag-Zn ore. Slags and soils contaminated with heavy metals (Zn; Pb; Cd; Fe; Mn; As) were the subject of this research. Samples were collected during archaeological works in the area of early medieval metallurgical settlement. The main goals of the analyses (Scanning Electron Miscroscopy-Energy Dispersive Spectroscopy (SEM-EDS); Electron Probe Microanalyzer (EPMA); X-ray diffraction (XRD); Atomic Absorption Spectroscopy (AAS)) were the determination of the mineralogical composition of furnace batches and smelting temperatures and conditions. In soils, the anthropogenic phases enriched in Pb, Zn, Fe, Mn, P, and primary minerals like goethite, ferrihydrite, sphalerite, galena, smithsonite, minrecordite, cerussite, gypsum, anglesite, jarosite, and hemimorphite were identified. The soil from former metallurgical settlements contained up to 1106 mg·kg−1 Pb, 782 mg·kg−1 Zn, 4.7 mg·kg−1 Cd in the fine fraction. Much higher heavy metal concentrations were observed in the waste products of ore rinsing, up to 49,282 mg·kg−1 Pb, 64,408 mg·kg−1 Zn, and 287 mg·kg−1 Cd. The medieval smelting industry and Pb-Ag-Zn ore processing are marked by highly anomalous geochemical pollution (Pb; Zn; Cd; Fe; Mn; Ba) in the topsoil. The methods of mineralogical investigation, such as SEM-EDS or EMPA, can be used to identify mineralogical phases formed during metallurgical processes or ore processing. Based on these methods, the characteristic primary assemblage and synthetic phases were identified in the area polluted by medieval metallurgy and mining of Pb-Ag-Zn ores, including MVT (Mississippi Valley Type) deposits. The minerals distinguished in slags and the structural features of metal-bearing aggregates allow us to conclude that batches have included mostly oxidised minerals (PbCO3; ZnCO3; CaZn(CO3)2; FeOOH), sulfides (PbS and ZnS) and quartz (SiO2). The laboratory experiment of high-temperature heating of the examined slags showed that smelting temperatures used in the second half of 13th century were very high and could have reached up to 1550◦ C. The results indicate, that geochemical and mineralogical methods can be used to obtain important information from archaeological sites, even after archaeological work has long ceased. © 2019 by the authors. Licensee MDPI, Basel, Switzerland.},

note = {21},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85071262697,

title = {Rainwater-induced migration of potentially toxic elements from a Zn–Pb slag dump in Ruda Śląska in light of mineralogical, geochemical and geophysical investigations},

author = { R. Warchulski and M.J. Mendecki and A. Gawęda and M. Sołtysiak and M. Gadowski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85071262697&doi=10.1016%2fj.apgeochem.2019.104396&partnerID=40&md5=b22dcb6041800cf693d9fc9a4ebcdb5b},

doi = {10.1016/j.apgeochem.2019.104396},

issn = {08832927},

year  = {2019},

date = {2019-01-01},

journal = {Applied Geochemistry},

volume = {109},

publisher = {Elsevier Ltd},

abstract = {The Upper Silesia region of Poland is known for its concentration of heavy industry, including mining and smelting. Slag dumps scattered across the region are the sources of pollutants such as Zn, Mn, As, Cd and Pb. At the slag dump in Ruda Śląska, it is possible to distinguish three types of slag: (i) slag associated with the muffle/lining material, composed of olivine, pyroxene, iron oxide, feldspar and glass; (ii) glassy slag composed of glass and single crystals of melilite and wollastonite; and (iii) slag composed of aggregates of melilite, wollastonite and anorthite. These concentrate Potentially Toxic Elements (PTEs), reaching up to 6130 mg/kg of As, 36300 mg/kg of Mn, 21700 mg/kg of Pb, 53600 mg/kg of Zn and 105 mg/kg of Cd. Rainfall-induced weathering causes PTE mobilisation to secondary phases, mainly carbonates, sulphates, oxides and hydroxides. Leaching tests based on the Synthetic Precipitation Leaching Procedure (SPLP) prove the release of PTEs from slags and secondary phases, which was further confirmed by significant PTE concentrations in a water sample from effluent next to the dump: 2710 μg/l Mn, 163 μg/l Zn, 52.5 μg/l Pb, 20.1 μg/l As, 0.98 μg/l Cd. This study is the first attempt to apply a combination of electromagnetic (EM) measurements and mineralogical investigations to pyrometallurgical Zn–Pb slags, and to precisely describe links between the obtained conductivity and in-phase results and phases building soils and sediments of the studied area. Contamination mapping, using combined scanning electron microscopy-energy dispersive spectrometry (SEM-EDS), X-ray diffraction (XRD) and EM methods, allowed to distinguish the main migration path of PTEs from the slag dump. This path is related to the effluent in which the presence of sulphides, oxides and hydroxides concentrating Cd, Zn, and Pb was determined to cause both high conductivity (>300 mS/m) and in-phase values (>6 ppt). On the other hand, soils from other areas outside the dump are not polluted by this migration path. Application of EM mapping confirmed its usefulness as a tool for tracking environmental contamination. For successful interpretation, however, it must always be used in combination with mineralogical/petrological methods. © 2019 Elsevier Ltd},

note = {13},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-85040554743,

title = {Geochemistry, petrology and evolutionary computations in the service of archaeology: restoration of the historical smelting process at the Katowice–Szopienice site},

author = { R. Warchulski and P. Juszczuk and A. Gawęda},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-85040554743&doi=10.1007%2fs12520-016-0435-8&partnerID=40&md5=1036c3eb10378cfa220122f85d552085},

doi = {10.1007/s12520-016-0435-8},

issn = {18669557},

year  = {2018},

date = {2018-01-01},

journal = {Archaeological and Anthropological Sciences},

volume = {10},

number = {5},

pages = {1023-1035},

publisher = {Springer Verlag},

abstract = {Activity at the smelting plant at Katowice–Szopienice dates back to the nineteenth century. Currently, the Museum of Zinc has been funded at the site. Unfortunately, as a result of unrest during both World Wars, all technological descriptions were lost. Three historically described samples were provided by Museum of Zinc and additional slag and lining samples were collected directly from the furnace. “Enriched ore” is dominated by ZnS (89.5%) as sphalerite and wurtzite accompanied by gangue minerals. “Roasted ore” is composed mainly of zincite (74%) resulting from the oxidation of ZnS. Study has proved that “roasted ore with coke” sample description is inappropriate. It is zinc depleted and enriched in Si (22.93 wt.%), Al (9.16 wt.%), C (9.66 wt.%) and its phase composition suggest that it contains recycled lining material and coke. Such characteristics place sample as additions used for smelting process. Advanced mathematical tool, the differential evolution algorithm, was used for restoration of smelting process at the site. Algorithm proved great usefulness by providing low dispersed results for calculated compositions of loss on smelting (mainly yield) with the fitting error reduced down to 1.19 wt.%. Loss on smelting composition was dominated by Zn (41.40 wt.%), Si (9.67 wt.%) and C (9.50 wt.%). Proportion of roasted ore to addition in smelting process was estimated as 1:1.27 and loss on smelting share from batch was 62%. Geochemistry and petrology have provided rich qualitative information about the samples and smelting process, but in combination with evolutionary computations, high-quality quantitative data were obtained. © 2016, The Author(s).},

note = {10},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-84961859357,

title = {Mineralogy and origin of coarse-grained segregations in the pyrometallurgical Zn-Pb slags from Katowice-Wełnowiec (Poland)},

author = { R. Warchulski and A. Gawęda and J. Janeczek and M. Kądziołka-Gaweł},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84961859357&doi=10.1007%2fs00710-016-0439-1&partnerID=40&md5=800a08fc08ff021df0041383b0bd385f},

doi = {10.1007/s00710-016-0439-1},

issn = {09300708},

year  = {2016},

date = {2016-01-01},

journal = {Mineralogy and Petrology},

volume = {110},

number = {5},

pages = {681-692},

publisher = {Springer-Verlag Wien},

abstract = {The unique among pyrometallurgical slags, coarse-grained (up to 2.5 cm) segregations (up to 40 cm long) rimmed by “aplitic” border zones occur within holocrystalline historical Zn-smelting slag in Katowice, S Poland. Slag surrounding the segregations consists of olivine, spinel series, melilite, clinopyroxene, leucite, nepheline and sulphides. Ca-olivines, kalsilite and mica compositionally similar to oxykinoshitalite occur in border zones in addition to olivine, spinel series and melilite. Miarolitic and massive pegmatite-like segregations are built of subhedral crystals of melilite, leucite, spinel series, clinopyroxene and hematite. Melilite, clinopyroxenes and spinels in the segregations are enriched in Zn relatively to original slag and to fine-grained border zones. The segregations originated as a result of crystallization from residual melt rich in volatiles (presumably CO2). The volatile-rich melt was separated during fractional crystallization of molten slag under the cover of the overlying hot (ca. 1250 °C) vesicular slag, preventing the escape of volatiles. That unique slag system is analogous to natural magmatic systems. © 2016, The Author(s).},

note = {10},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-84992187787,

title = {Zn-Pb slag crystallization: Evaluating temperature conditions on the basis of geothermometry},

author = { R. Warchulski},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84992187787&doi=10.1127%2fejm%2f2015%2f0027-2496&partnerID=40&md5=8608ab4ed5c0299a2e234858283d5b8b},

doi = {10.1127/ejm/2015/0027-2496},

issn = {09351221},

year  = {2016},

date = {2016-01-01},

journal = {European Journal of Mineralogy},

volume = {28},

number = {2},

pages = {375-384},

publisher = {Gebruder Borntraeger Verlagsbuchhandlung},

abstract = {Temperature estimates are key to understanding the crystallization of pyrometallurgical slags. To date, temperature approximations have been based mainly on phase diagrams; these give approximate data only. Geothermometers (e.g.; phase - whole-rock composition) applied in this study give much more accurate, focused results that are in agreement with historical data. Pyrometallurgical slags related to zinc extraction in Upper Silesia, southern Poland, date back to the 19th century. Thus, there is a great variety of slag textures and compositions reflecting changes in technological processes ranging from the primitive "Silesian method" to more advanced techniques including calcination and precise dosages of coal/coke and add-ons. Slag samples were collected at three localities with known smelting histories: Piekary Śląskie, Katowice and Ruda Śląska. The analysed material is composed of high-temperature phases among which oxides, silicates and aluminosilicates dominate. The chemical composition of the slags is complex, with up to nine major oxide components, namely, SiO2, Al2O3, FeOt, ZnO, PbO, MnO, MgO, CaO and K2O. The three geothermometers applied, i.e., olivine - WR (whole rock), pyroxene - WR and feldspar - WR, yielded temperatures ranging from 987 to 1314°C. Phase diagrams on the other hand, due to the complex chemical compositions involved, were useful for general determinations only; they gave overestimated temperatures in the range 1100-1800°C. Evaluating temperature conditions using geothermometry demonstrated the usefulness of different technological processes at the various sites sampled. © 2015 E. Schweizerbart'sche Verlagsbuchhandlung.},

note = {12},

keywords = {},

pubstate = {published},

tppubtype = {article}

}

@article{2-s2.0-84946061825,

title = {Composition and element mobilization in pyrometallurgical slags from the Orzeł Biały smelting plant in the Bytom-Piekary ͆laskie area, Poland},

author = { R. Warchulski and A. Gawęda and M. Kądziołka-Gaweł and K. Szopa},

url = {https://www.scopus.com/inward/record.uri?eid=2-s2.0-84946061825&doi=10.1180%2fminmag.2015.079.2.21&partnerID=40&md5=18374edf64b8f8e38b0410f000a9c6bd},

doi = {10.1180/minmag.2015.079.2.21},

issn = {0026461X},

year  = {2015},

date = {2015-01-01},

journal = {Mineralogical Magazine},

volume = {79},

number = {2},

pages = {459-483},

publisher = {Mineralogical Society},

abstract = {Wastes accumulated at Piekary ͆l?skie, Poland, are the result of 150 years of continuous working of the Orzeł Biały smelting plant. Slags are composed of: oxides (spinel; hematite; zincite); silicates and aluminosilicates (olivine; monticellite-kirschteinite; titanite; merwinite; pyroxene; melilite; feldspars: plagioclases and plumbean K-feldspar; nepheline; kalsilite; leucite); sulfides (pyrrhotite; rudashevskyite; galena), metallic phases (pure iron and iron-arsenic mixture) and secondary phases (gypsum; rapidcreekite; apatite). Interstices between the crystalline phases are filled by glass, concentrating toxic and potentially harmful elements, e.g. up to 53.22 wt.% PbO. The sequence of crystallization of primary phases depended on the local variability of oxygen fugacity and degree of calcination, while the texture type resulted from the cooling time and partial pressure of volatiles. Suggested crystallization temperatures are in the range of 1200-1500°C. Bulk chemical analyses show that the slags are composed mainly of SiO2, Al2O3,Fe2O3, MgO and CaO. Among the potentially harmful elements, Zn is the most common, reaching up to 5.93 wt.%, Pb is present in concentrations up to 3.9 wt.% and As in weathered samples exceeds 1 wt.%. Leaching tests of these elements confirms As mobility as Zn and Pb are preferably leached from fresh slags, while As is present in greater amounts in leachate from weathered slag samples. The documented amounts of As, Zn, Pb and their mobility in slags produce an environmental risk, as this material is currently used widely for commercial purposes. © 2015 Mineralogical Society 2015.},

note = {27},

keywords = {},

pubstate = {published},

tppubtype = {article}

}